Activated single bath pearl gray chrome green mineral dyeing and composition therefor

ABSTRACT

Conventional &#39;&#39;&#39;&#39;pearl gray&#39;&#39;&#39;&#39; chrome green mineral dyes require a double decomposition process for depositing green chromium oxide in cellulosics. By forming a unique alkaline complex of a chromic chloride with ammonium oxalate and zirconyl ammonium carbonate, a single dye bath is produced, enabling the dyes to apply the &#39;&#39;&#39;&#39;pearl gray&#39;&#39;&#39;&#39; chrome green mineral dyeing by a simple pad, dry, cure, and wash procedure. The dyeings are uniform and the cellulosic is not tendered or physically degraded. Not only does this invention reduce processing steps, but it eliminates the conventional problem of tendering resulting from drying the chromic chloride on cellulosics prior to processing through a second bath of soda ash and soap. The invention makes it possible to prepare a modified chromic chloride stock solution that can be used for either the conventional &#39;&#39;&#39;&#39;pearl gray&#39;&#39;&#39;&#39; processing or the single bath process described above.

United States Patent 1 Conner 51 Oct. 30, 1973 [75] Inventor:

[73] Assignee: The United States of America as represented by theSecretary of Agriculture, Washington, D.C.

[22] Filed: Aug. 31, 1971 [21] Appl. No.: 176,736

Charles J. Conner, Metairie, La.

[52] U.S. Cl 8/17, 8/52, 106/304,

[51] Int. Cl C09b 61/00 [58] Field ofSearch "r 8/17, 52

[56] References Cited UNITED STATES .PATENTS 2,091,539 l/l935 White 8/76X 2,035,527 7/1932 3,431,059 3/1969 2,202,328 5/1940 2,229,923 1/1941Primary Examiner-Harold Ansher Assistant Examiner-Patricia C. IvesAtto'meyR. Hoffman et a1.

57 ABSTRACT Conventional pearl gray chrome green mineral dyes require adouble-decomposition process for depositing green chromium oxide incellulosics. By forming a unique alkaline complex of a chromic chloridewith ammonium oxalate and zircon-yl ammonium carbonate, a single dyebath is produced, enabling the dyes to apply the pearl gray" chromegreen mineral dyeing by a simple pad, dry, cure, and wash procedure. Thedyeings are uniform and the cellulosic is not tendered or physicallydegraded. Not only does this invention reduce processing steps, but iteliminates the conventional problem of tendering resulting from dryingthe chromic chloride on cellulosics prior to processing through a secondbath of soda ash and soap. The invention makes it possible to prepare amodified chromic chloride stock solution that can be used for either theconventional pearl gray" processing or the single bath process describedabove.

6 Claims, No Drawings hereby granted to the Government of the UnitedStates of America.

It has been known from prior art that chromic chloride reacts withalkali hydroxides and carbonates to produce a precipitate of hydratedchromium oxide, having a grayish-green color, and referred to in mineraldyeing terminology as pearl gray. When a cellulosic is wetted withchromic chloride, dried, and then wetted with an alkali hydroxide orcarbonate solution, this precipitated hydrated chromium oxide isdesposited in the cellulosic to attribute a gray-green color (mineraldyeing). The prior art teaches that this wet dyed cellulosic must thenbe washed, treated with fungicide and then dried. I

The present invention consists of treating the chromic chloride withammonium oxalate and an ammoniacal solution, which produces an'alkalineaqueous soluble complex of hydrated chromium oxide with ammoniumoxalate. When zirconyl ammonium carbonate is used with ammoniumhydroxide, a water soluble chromium zirconium hydrated oxide complex isproduced with the excess ammoniacal alkalinity. When this solution(bath) is applied to cellulosics, and the cellulosics heated to drynessand cured at temperatures of 130C to 150C, the hydrated zirconia andgreen chromium oxide are deposited as an insoluble residue to produce auniform mineral dyeing. When copper metaborate, copper hydroxide, orcopper carbonate is solubilized in the ammonium hydroxide, priortoaddition to the formulation, the bath is compatible, and a fungicidalpearl gray mineral dyeing is deposited in cellulosics by heat curing.

The main object of the invention is to provide a single-bath chromemineral dye bath from conventional chromic chloride to eliminate doubledecomposition baths and produce uniform pearl-gray" mineral dyeings by asimple pad, dry, and cure procedure, followed by wash and dry to removebyproducts.

A second object of the invention is to provide a single modified chromicchloride stock solution, which can be used for single bath orconventional pearlgraymineral dyeing.

A third object of the invention is to provide a single dye bath fromchromic chloride and 'copper compounds, to produce fungicidal pearl-graymineral dyeings by a simple pad, dry, and cure procedure.

I A fourth object of the invention is to provide a single bath fromchromic chloride, copper compounds, and paraffin-ammonium stearateemulsion components to deposit a fungicidal pearl-gray mineral dyeingwith water repellent finish, by a simple pad, dry, and cure procedure.

The prior art teaches that chromic chloride will degrade and tendercellulosics when heat dried on them. This invention enables the use ofchromic chloride in ammoniacal zirconium complex without tendering ordegrading the cellulosic. The prior art also teaches that conventionalpearl-gray mineral dyeing requires a double decomposition procedure,followed by a treatment with fungicide. the present invention appliesthe mineral dyeing and fungicide from the same single bath system. Theprior art teaches that conventional water repellent finishes are appliedlast to the dye and fungicide treated cellulosic. The present inventionincorporates the wax finish in with the dye and fungicide, in a singlebath, to produce fungicidal mineral dyeings with water repellent finishby a simple pad, dry, and cure procedure.

Utility of the invention is obviously in the field of mineral dyeingsand weatherable goods, such as for tents, sails, tarpaulins, umbrellas,awnings, rope, shoe lining, rainwear, boat covers, canvas shoes,upholstery, etc.

The following examples are presented to illustrate the invention andcertain aspects of its usefulness. These are not to be interpreted aslimiting the invention in any manner whatever. The treatments were alsoapplied to paper, porous ceramics, wood,.and other fabrics havingcellulosic compositions.

I EXAMPLE l Four stock solutions of chromic chloride, having chromiummetal contents of 8, 10, 15, and 16 percent were formulated into thefollowing formula:

25 .00 grams chromic chloride stock (8 10 percent Cr) 25.00 grams water(distilled 4.00 grams ammonium oxalate crystals (fine) 20.00 gramszirconyl ammonium carbonate (10% ZI'Oz) 5.00 grams ammonium hydroxide(29.4 percent N a) 79.00 grams single bath The 8 and 10 percent chromicchloride stock solutions were compatible while the 15 and 16 percentstock solutions produced gelatinous gray-green precipitates, and wereincompatible. The chromic chloride chromium content is a limitingfactor, and cannot exceed 10 percent, being desirable at 8 percentchromium.

EXAM PLE 2 results.

EXAM PLE 3 The following formulation represents a single bath systemwith an 8% Cr chromic chloride stock and copper metaborate to produce afungicidal pearlgray mineral dyeing:

25.0 grams chromic chloride (8 percent Cr content) 25.0 grams water i2.0 grams copper metaborate (40 percent Cu) 4.0 grams ammonium oxalatecrystals (fine) 20.0 grams zirconyl ammonium carbonate percent ZTOz) 5.0grams ammonium hydroxide (29.4 percent N 3) 81.0 grams single bath(fungicide-mineral dye) EXAMPLE 4 The bath from Example 1 (with 8percent chromic chloride stock formulation) was used to wet severalpieces of 4 X 8 inch scoured 9 oz. army duck. The wetted duck wasblotted and oven dried at 110 to 120C. for 2 to 4 minutes, followed byoven curing at 130 to 140C for 2 to 3 minutes. The cured fabric was dyeda deep gray-gree rfminefafiyeing (pear l gray). The cured samples werewashed in both hot and cold running tap water and oven dried at l10-120Cfor 2 to 4 minutes. The fabrics remained a deep gray-.' 1

green dyed color shade,and were stable to water washings.

EXAMPLES The bath from Example 3 was similarly applied to samples of 9oz. army scoured duck, using the procedures of Example 4. The duck wasdyed a deep grayish-green (pearl gray) mineral dyeing, having a copper(fungicidal) content of 0.5 percent Cu.

EXAMPLE6 Preparation of modified chromic chloride," which can be usedfor'single bathapplication per Examples 1 through 5, or for conventionalpearl gray mineral dyeings:

25.00 grams percent Cr) 25.00 grams distilled water 4.00 grams ammoniumoxalate crystals (fine) 54.00 grams modified stock chromic chloride Theammonium oxalate is dissolved in the 50 grams of chromic chloride andwater and retained for use in conventional (double decomposition) pearlgray dyeing, or for further addition of zirconyl ammonium carbonate (10percent ZrO2) and ammonium hydroxide (29.4 percent NH3) for single bathpearl gray mineral dyeings. The modified stock is a clear greenish-blacksolution, which is activated by adding the ammoniacal components, andcopper metaborate (if desired).

chromic chloride stock(8l0 EXAMPLE 7 to 2 percent soft soap (potassiumstearate or comparable) to the soda ash bath assures better lock-on anda greener shade of color.

b. Single Bath Dyeing: A 4 X 6 inch sample of scoured duck was treatedwith the further modification of the Example 6 stock:

54.00 grams modified chromic chloride" (Example 6) 20.00 grams zirconylammonium carbonate (10 percent ZrO 5.00 grams ammonium hydroxide (29.4percent NHQ) 79.00 grams single bath (pearl gray) The drying and curingprocedure were the same as in Example 4. A deep gray-green mineraldyeing resulted.

EXAMPLE 8 A sample of the scoured duck treated in Example 3 (with coppermetaborate-chromic chloride comples with zirconium) was soil buried forone week with a piece of untreated scoured duck (control). After 4weeks, the control fabric had-rotted out, while the treated fabricretained 20 percent strength.

EXAM PLE 9 Samples from the single bath treatments in Examples 4, 5, and7 (conventional) were exposedon the weather rack for 6 months along withuntreated scoured duck. No growths were evidenced on the treatedsamples, while algae and mildew growths were noted on the controlsample.

The washed fungicidally dyed fabrics produced according to Examples 4and 5 can be wax finished by conventional paddings through a 7 to 9percent paraf- 5 fin (paraffin-ammonium stearate emulsion) to obtain 3oven dry-cured at 135l40C for 3 to 4 minutes,

followed by a 1 to 2 minute tap water rinse and oven drying at 130C for2 minutes. The fabric was mineral dyed a gray-green color. The additionof l to 4 percent paraffin add-ons, followed by oven dry at 1 10 to 120Cfor 2 minutes and oven curing at to C to melt the paraffin into thefabric and decompose the ammonium stearate. The NH, leaves the fabric asgas, and the stearic acid combines with the zirconia to producezirconium stearate.

The aqueous 7 to 9 weight percent paraffin ammo nium stearate emulsioncan be conveniently prepared by diluting, with effective stirring, 2,000grams of a commercially available paraffin-ammonium stearate waxemulsion paste with 8,000 grams of water. This will produce 10,000 gramsof a paraffin wax pad bath containing about 7 weight percent of paraffinwax.

EXAMPLE 10 The washed-dyed fabrics from Examples 4 and 5 were wettedwith an 8 percent paraffin-paraffin ammonium stearate emulsion, blottedfree of excess liquid, and oven dried for 2 minutes at 120C. The driedfabric then curved at 145 150C for 2 minutes, and allowed to conditionat room temperature (250C) for l hour. Thetreated fabric was completelyater repellent, spray rating 90 to 100. This example was repeated in thepilot plant in four runs: wherein the emulsion was applied byconventional padding, and drying and curing effected in a continuousoven-tenter frame operation, using 110C for 2 minutes in drying, and150C for 2 minutes in curing. The same excellent water repellencyresulted.

I claim: I

1. An activated, water-based composition of matter useful to effectpearl gray chrome green mineral dyeing, said dyeing exhibitingfungicidal properties, which copper.

2. An activated, water-based composition of matter according to claim 1wherein the copper compound is copper metaborate.

3. An activated, water-based composition of matter according to claim 1wherein the copper compound is copper carbonate.

4. An activated, water-based composition of matter according to claim 1wherein the copper compound is copper hydroxide.

5. A single bath mineral dyeing process for a cellulosic materialproviding ancillary fungicidal properties to the said material andconsisting of the following steps:

a. wetting the cellulosic material with the water based composition ofclaim 1;

b. oven-drying the wetted material from step (a) at a temperatureof from1 10to C for a period offrom 2 to 4 minutes;

c. oven-curing the dried material from step (b) at a temperature of fromto C for a period of from 2 to 4 minutes:

. water washing the cured material from step (c) for a period of from 2to 4 minutes; and e. oven-drying the washed material from step (d) at atemperature of from .1 10 to 120C for a period of from 2 to 4 minutes.

6. A process according to claim 5 wherein the dried and washed materialfrom step (e) thereof is rendered water repellent by the stepscomprising:

a. wetting the said material with a paraffinammonium stearate emulsioncontaining about from 7 to 9 weight percent of paraffin;

- b. drying the wetted material from step (a) at a temperature of aboutl20iC for about 2 minutes, and

c. curing the dried material of step (b) ata temperature of from 145 toC for a period of about 2 minutes.

2. An activated, water-based composition of matter according to claim 1wherein the copper compound is copper metaborate.
 3. An activated,water-based composition of matter according to claim 1 wherein thecopper compound is copper carbonate.
 4. An activated, water-basedcomposition of matter according to claim 1 wherein the copper compoundis copper hydroxide.
 5. A single bath mineral dyeing process for acellulosic material providing ancillary fungicidal properties to thesaid material and consisting of the following steps: a. wetting thecellulosic material with the water based composition of claim 1; b.oven-drying the wetted material from step (a) at a temperature of from110* to 125* C for a period of from 2 to 4 minutes; c. oven-curing thedried material from step (b) at a temperature of from 130* to 145* C fora period of from 2 to 4 minutes; d. water washing the cured materialfrom step (c) for a period of from 2 to 4 minutes; and e. oven-dryingthe washed material from step (d) at a temperature of from 110* to 120*C for a period of from 2 to 4 minutes.
 6. A process according to claim 5wherein the dried and washed material from step (e) thereof is renderedwater repellent by the steps comprising: a. wetting the said materialwith a paraffin-ammonium stearate emulsion containing about from 7 to 9weight percent of paraffin; b. drying the wetted material from step (a)at a temperature of about 120* C for about 2 minutes, and c. curing thedried material of step (b) at a temperature of from 145* to 150* C for aperiod of about 2 minutes.